Acid polyazo dyes

ABSTRACT

PCT No. PCT/EP96/05632 Sec. 371 Date Jun. 19, 1998 Sec. 102(e) Date Jun. 19, 1998 PCT Filed Dec. 16, 1996 PCT Pub. No. WO97/24405 PCT Pub. Date Jul. 10, 1997Polyazo dyes of the formula where n, Y1, Y2, Y3, Y4, X, R1, R2 and R3 are each as defined in more detail in the description are useful for dyeing natural or synthetic substrates.

The present invention relates to novel polyazo dyes of the formula I ##STR2## where

n is 0 or 1,

Y¹ is hydrogen, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or SO₂ --Alk, SO₂ --Ar, SO₂ --N(Alk)₂, SO₂ --N (Alk)Ar, SO₂ --OAr, SO₂ --C₂ H₄ --Q, SO₂ --CH═CH₂, SO₂ --CH₂ CH═CH₂, CO--Ar, ##STR3## Y² is nitro, SO₂ --NHAr or Y¹, Y³ is hydrogen, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula SO₂ --Alk, SO₂ --N(Alk)₂, SO₂ --NHAlk, SO₂ --CH₂ COOH, SO₂ --C₂ H₄ --Q, SO₂ --CH═CH₂, SO₂ --CH₂ CH═CH₂, CO--Ar or CO--NHAlk or Y³ and Y² together are L--NZ--CO,

Y⁴ is hydrogen, or Y⁴ and Y³ together are L--NZ--CO,

X is hydrogen or C₁ -C₄ -alkyl,

R¹ is hydrogen, C₁ -C₄ -alkyl, halogen, carboxyl, C₁ -C₄ -alkoxycarbonyl or hydroxysulfonyl,

R² is hydrogen, C₁ -C₄ -alkyl, halogen, carboxyl or C₁ -C₄ -alkoxycarbonyl, or R² and R¹ together are L--NZ--CO,

R³ is hydrogen, hydroxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkanoyloxy or benzoyloxy, and

R⁴ is amino or hydroxyl, where

Alk is C₁ -C₈ -alkyl which can be interrupted by 1-3 oxygens in ether function or by sulfur or sulfonyl and can be substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carboxyl or phenyl,

Ar is phenyl which can be substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, carboxyl, C₁ -C₄ -alkanoylamino or hydroxysulfonyl,

L is methylene or carbonyl,

Z is hydrogen, naphthyl, C₅ -C₈ -cycloalkyl, Alk or Ar, and

Q is hydroxyl or a group which can be eliminated under alkaline conditions,

and also to their use for dyeing natural or synthetic substrates.

It is an object of the present invention to provide novel polyazo-class acid dyes having advantageous performance properties.

We have found that this object is achieved by the above-defined polyazo dyes of the formula I.

R¹, R², X, Y¹, Y², Y³ and Y⁴ are each present twice independently in the above formula I, and can therefore be identical or different at each occurrence.

If Y² and Y³ or Y³ and Y⁴ together are L--NZ--CO, this radical can at each occurrence be attached either via L or via CO to the ring positions of Y², Y³ and Y⁴.

Any alkyl in formula I can be either straight-chain or branched.

Any substituted alkyl radical in formula I generally has one or two substituents.

Any alkyls in the above formulae which are interrupted by oxygens in ether function preferably comprise one or two such oxygens.

Any substituted phenyls in the above formulae generally have 1-3 substituents.

R¹, R², X and Alk are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

Further examples of Alk are pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl (which is a trivial name derived from the alcohols obtained by oxo synthesis--cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 1, 290-293, and Vol. A 10, 284 and 285), 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 2-methylthioethyl, 2-ethylthioethyl, 2- or 3-methylthiopropyl, 2- or 3-ethylthiopropyl, 2- or 4-methylthiobutyl, 2- or 4-ethylthiobutyl, 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2- or 3-methylsulfonylpropyl, 2- or 3-ethylsulfonylpropyl, 2- or 4-methylsulfonylbutyl, 2- or 4-ethylsulfonylbutyl, chloromethyl, 2-chloroethyl, 2- or 3-chloropropyl, benzyl, 1- or 2-phenylethyl, 3-benzyloxypropyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 3-isobutyryloxypropyl, carboxylmethyl, 2-carboxylethyl, 2- or 3-carboxylpropyl,-2-sulfatoethyl or 2- or 3-sulfatopropyl.

Further examples of R¹ and R² are fluorine, chlorine, bromine, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl or butoxycarbonyl.

Examples of Ar are phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-isopropylphenyl, 2-, 3- or 4-butylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isobutoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-formylaminophenyl, 2-, 3- or 4-acetylaminophenyl, 2-, 3- or 4-propionylaminophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-carboxyphenyl or 2-, 3- or 4-hydroxysulfonylphenyl.

Examples of Z are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Examples of R³ are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, formyloxy, acetyloxy, propionyloxy, butyryloxy and isobutyryloxy.

Q is hydroxyl or a group which can be eliminated under alkaline conditions, for example chlorine, bromine, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, OSO₃ H, SSO₃ H, OP(O)(OH)₂, C₁ -C₄ -alkylsulfonyloxy, phenylsulfonyloxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -dialkylamino or a radical of the formula ##STR4## where W¹, W² and W³ are identical or different and independently are each C₁ -C₄ -alkyl or benzyl and each An⊖ is one equivalent of an anion. Examples of suitable and possible anions in this context are fluoride, chloride, bromide, iodide, mono-, di- and trichloroacetate, methylsulfonate, phenylsulfonate and 2- or 4-methylphenylsulfonate.

Examples of Y¹ are N-phenyl-N-methylsulfamoyl, N-phenyl-N-ethylsulfamoyl, N-phenyl-N-propylsulfamoyl, N-phenyl-N-butylsulfamoyl, 3-methyl-, 3-ethyl-, 3-propyl-, 3-butyl- or 3-phenyl-1,2,4-oxadiazol-5-yl, phenoxysulfonyl, 2-, 3- or 4-methylphenoxysulfonyl, phenylsulfonyl, 2-, 3- or 4-methylphenylsulfonyl or 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenylsulfonyl.

Examples of Y³ and additional examples of Y¹ are dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, bis(2-hydroxyethyl)sulfamoyl, bis(carboxymethyl)sulfamoyl, bis(2-carboxyethyl)sulfamoyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, 2-hydroxyethylsulfonyl, 2-chloroethylsulfonyl, 2-sulfatoethylsulfonyl, benzoyl-, 2-, 3- or 4-methylbenzoyl or 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylbenzoyl.

Further examples of Y³ are methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, isopropylsulfamoyl, butylsulfamoyl, 2-hydroxyethylsulfamoyl, carboxymethylsulfamoyl, 2-carboxyethylsulfamoyl, methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, isopropylcarbamoyl, butylcarbamoyl, 2-hydroxyethylcarbamoyl, carboxymethylcarbamoyl and 2-carboxyethylcarbamoyl.

Examples of Y² are phenylsulfamoyl and 2-, 3- or 4-methylphenylsulfamoyl.

Each ##STR5## is, for example, of the formulae ##STR6##

Since the polyazo dyes of the formula I comprise a plurality of hydroxysulfonyl groups, the invention also embraces the salts thereof.

Suitable salts in this context are metal salts or ammonium salts, the former being, in particular, lithium, sodium or potassium salts. Ammonium salts in the context of the invention mean salts having either unsubstituted or substituted ammonium cations. Examples of the latter are mono-, di-, tri-, tetra- or benzyltri-alkylammonium cations or those derived from N-containing five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium or piperazinium cations or their N-monoalkyl- or N,N-dialkyl-substituted products. Alkyl in this case is generally straight-chain or branched C₁ -C₂₀ -alkyl which can be mono- or disubstituted by OH and/or interrupted by 1-4 oxygens in ether function.

Preference is given to polyazo dyes of the formula Ia ##STR7## where Y¹, Y², Y³, Y⁴, X, R¹, R² and R³ are each as defined above.

Preference is further given to polyazo dyes of the formula Ib ##STR8## where Y¹, Y², Y³, Y⁴, X, R¹, R² and R³ are each as defined above.

Preference is further given to polyazo dyes of the formula I where R¹ and R² are each hydrogen, and to those where Y¹ is hydrogen, hydroxysulfonyl or ##STR9## where each Ar is as defined above, and to those where Y² is hydrogen, hydroxysulfonyl, nitro or SO₂ --N(Alk)2, SO₂ --C₂ H₄ --Q or SO₂ --CH═CH₂, where Alk and Q are each as defined above, and to those in which Y³ is hydrogen, hydroxysulfonyl or SO₂ --C₂ H₄ --Q or SO₂ --CH═CH₂ or Y³ and Y² together are L--NZ--CO, where L, Q and Z are each as defined above, and to those in which Z is unsubstituted or OH-substituted C₁ -C₄ -alkyl or is phenyl.

Particular preference is given to polyazo dyes of the formula I where X is hydrogen, and to those where R³ is hydroxyl.

Very particular preference is given to polyazo dyes of the formula I where R¹ and R² are each hydrogen and R³ is hydroxyl.

Of particular technical interest are polyazo dyes of the formula Ic ##STR10## where Y¹, Y², Y³ and Y⁴ are each as defined above.

Preference is furthermore given to polyazo dyes of the formula I where the substituents are selected from a combination of the preferred ones above.

The novel polyazo dyes of the formula I can be obtained by methods known per se; those where n is 0, for example, by first diazotizing an aniline of the formula II ##STR11## where Y¹, Y², Y³ and Y⁴ are each as defined above, and coupling the resulting diazonium salt with 1-amino-8-hydroxynaphthalene-3,5- or -3,6-disulfonic acid.

The resulting monoazo dye of the formula III ##STR12## where Y¹, Y², Y³ and Y⁴ are each as defined above, can then be coupled, again in a manner known per se, with a diazonium salt that can be obtained by conventional diazotization of a sulfonyl compound of the formula IVa ##STR13## where R¹, R², R³ and X are each as defined above, to give disazo dyes of the formula V ##STR14## where R¹, R², R³, yl, Y², Y³, Y⁴ and X are each as defined above.

In a further reaction the tetrazonium salt that can be obtained by conventional tetrazotization of a sulfonyl compound of the formula IVb ##STR15## where R¹, R² and X are each as defined above, can be coupled first with the monoazo dye III and then with the disazo dye V, to give the polyazo dyes of the formula I.

To prepare dyes I where n is 1 it is possible, for example, to couple the tetrazonium salt obtainable by conventional tetrazotization of a sulfonyl compound of the formula IVc ##STR16## where R¹, R², R³ and X are each as defined above, first with the monoazo dye III and then with an amine of the formula VI ##STR17## where R⁴ is as defined above.

The resulting polyazo dye can then be coupled with the product of the reaction between the tetrazonium salt resulting from the sulfonyl compound IVb and the monoazo dye III.

The novel polyazo dyes of the formula I are advantageously suitable for dyeing natural or synthetic substrates, for example wool, leather, polyamide or paper (for example by means of the inkjet process). They are particularly suitable for dyeing leather.

The dyeings obtained have greenish to reddish blue hues and good migration and wet fastness properties.

The novel dyes can be used not only alone but also mixed with one another or with other dyes, especially with C.I. Acid Black 210.

The examples which follow are intended to illustrate the invention.

EXAMPLE 1

a) 32.8 g of the diazo component of the formula ##STR18## were dissolved in 250 ml of water at 80° C. with sodium hydroxide solution at a pH of 11-11.5. 1.5 g of a dispersant and 40 ml of 23% strength by weight aqueous sodium nitrite solution were added. The resulting suspension was stirred in 300 ml of water and 40 ml of concentrated hydrochloric acid and then subsequently stirred at 40-45° C. for 4 hours. Excess nitrous acid was then destroyed.

b) 38.35 g of 83.2% strength by weight aqueous 1-amino-8-hydronaphthalene-3,5-disulfonic acid were dissolved in 150 ml of water with sodium hydroxide solution at a pH of 6.0-6.5. This solution was then added dropwise over the course of 90 minutes to the diazonium salt suspension described under a) and coupling was carried out at 30-40° C. The reaction mixture was subsequently stirred overnight.

c) 26.5 g of the diazo component of the formula ##STR19## were suspended in a conventional manner with 50 ml of 18.5% strength by weight hydrochloric acid, and the mixture was cooled with ice to -2° C. and then tetrazotized at 0-5° C. using 31 ml of 23% strength by weight aqueous sodium nitrite solution. Stirring was carried out subsequently for 1 hour, excess nitrous acid was destroyed, and the tetrazonium salt solution was run over the course of 1 hour into the reaction mixture described under b) at a rate such that the pH was maintained continuously at >4-7.5 (addition of sodium hydrogen carbonate), giving a blue dye of the formula ##STR20##

d) 18.4 g of the diazo component of the formula ##STR21## were diazotized in a conventional manner with 35 ml of concentrated hydrochloric acid, ice and 31 ml of 23% strength by weight aqueous sodium nitrite solution. Following the destruction of excess nitrite, the solution obtained was added to 31.9 g of a 10% strength by weight aqueous, freshly prepared suspension of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid with a pH of 0.8-1.0. Coupling of the mixture was allowed to proceed to completion overnight. Then 26.4 g of the tetrazo component of the formula ##STR22## were tetrazotized in a manner known per se at 0-5° C. with hydrochloric acid and sodium nitrite. The resulting tetrazonium salt solution was run at a pH of from >5 to not more than 9 into the reaction mixture described above under d) and coupled to give the disazo dye of the formula ##STR23##

e) The blue coupling product described under c) was dissolved with sodium hydroxide solution at a pH of 10.5-11. The reaction mixture described under d) was run into this solution over the course of 1 hour at a pH of ≧10.5-11 and at 5-10° C., and the pH was held at this level. After coupling to completion, a navy dye of the formula ##STR24## was present. Precipitation with potassium chloride at a pH of 1-4, filtration with suction and drying of the product gave 175 g of dye containing about 65 g of sodium chloride, potassium chloride and about 2.5% by weight of water. The dye dissolves in water with a reddish blue hue and dyes wool and leather in a blue to navy shade with very good fastness properties.

EXAMPLE 2

78.7 g of the dye of the formula ##STR25## were suspended in 250 ml of water and the suspension was adjusted with sodium hydroxide solution to a pH of 10.5-11.0. 91.3 g of the diazonium salt of the formula ##STR26## which was prepared by a method known per se, were added dropwise in the form of an aqueous suspension to this mixture at 20-25° C., over the course of 1.5 hours, at a rate such that the pH of the reaction mixture was held at 10.5-11 with sodium carbonate. The mixture was subsequently stirred overnight at 20-25° C. and at a pH of 10.2-11.0. It was then heated to 75° C., and the dye of the formula ##STR27## was precipitated with hydrochloric acid at a pH of <5-0.5. Filtration with suction and drying of the product gave 220 g of a black powder which contained about 30 g of salt and 10 g of water.

The dye dissolves in water with a blue hue and dyes wool in a wet-fast reddish blue to navy shade. The strong, reddish blue dyeings obtained on leather are also wetfast and have excellent migration fastness and good light fastness.

The absorption spectrum of a solution in aqueous acetic acid shows a maximum at 594 nm and a minimum at 430 nm.

The dyes listed below are obtained analogously.

    TABLE 1        -       ##STR28##      Ex. No. Y.sup.11 Y.sup.21 Y.sup.31 Y.sup.12 Y.sup.22 Y.sup.32        3 H SO.sub.2 OC.sub.6       H.sub.5 H H NO.sub.2 H                            4 H NO.sub.2 H H      SO.sub.2 OC.sub.6       H.sub.5 H                                               5 SO.sub.2      C.sub.6       H.sub.5 H H H NO.sub.2 H                                          6      SO.sub.2 C.sub.6 H.sub.5 H H SO.sub.2 C.sub.6       H.sub.5 H H                 7 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.3 H      SO.sub.2 C.sub.6       H.sub.5 H H                      8       ##STR29##       H SO.sub.3 H SO.sub.2 C.sub.6       H.sub.5 H H                                    9       ##STR30##       H SO.sub.2       CH.sub.3      ##STR31##       H H      10       ##STR32##       H H       ##STR33##       H SO.sub.2       CH.sub.3                 11       ##STR34##       SO.sub.3       H H H NO.sub.2 H              12       ##STR35##       SO.sub.3 H H SO.sub.2 C.sub.6 H.sub.5 H SO.sub.2 CH.sub.2 CO.sub.2 H                                                                            13       ##STR36##       SO.sub.3       H H      ##STR37##       H SO.sub.2       CH.sub.3                 14 H SO.sub.2 CH.sub.2 CH.sub.2       OH H H NO.sub.2 H              15 H SO.sub.2 CH═CH.sub.2 H H      NO.sub.2 H        16 H SO.sub.2 CH═CH.sub.2 H H SO.sub.2       CH═CH.sub.2 H            17 H H SO.sub.2 CH═CH.sub.2 H SO.sub.2        CH═CH.sub.2 H        18 H NO.sub.2 H H SO.sub.2       CH═CH.sub.2 H                            19 H NO.sub.2 H H H      SO.sub.2       CH═CH.sub.2                                                  20 H      SO.sub.2 C.sub.6       H.sub.5 H H NO.sub.2 H                      21 H       ##STR38##       H H NO.sub.2 H      22 H SO.sub.2 OC.sub.6 H.sub.5 H H SO.sub.2       CH═CH.sub.2 H             23 H NO.sub.2 H H SO.sub.2 C.sub.6      H.sub.5 H      24 H NO.sub.2 H H       ##STR39##       H      25 H NO.sub.2 H H       ##STR40##       H      26 H NO.sub.2 H H SO.sub.2 N(C.sub.2 H.sub.4       OH).sub.2 H                                                  27 H       ##STR41##       H H NO.sub.2 H      28 H SO.sub.2 N(C.sub.2 H.sub.4       OH).sub.2 H H NO.sub.2 H                                     29       ##STR42##       SO.sub.3 H H H SO.sub.2       CH═CH.sub.2 H                              30       ##STR43##       SO.sub.3 H H H SO.sub.2       CH═CH.sub.2 H                              31 COC.sub.6 H.sub.5 SO.sub.3 H H H SO.sub.2      CH═CH.sub.2 H      32       ##STR44##       H H H SO.sub.2       CH═CH.sub.2 H                     33       ##STR45##       SO.sub.3 H H H H SO.sub.2       CH═CH.sub.2                                34 H SO.sub.2       CH═CH.sub.2 H      ##STR46##       SO.sub.3       H H              35 H H SO.sub.2       CH═CH.sub.2      ##STR47##       SO.sub.3       H H              36 SO.sub.3 H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H H NO.sub.2 H         37 SO.sub.3 H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H H SO.sub.2       CH═CH.sub.2 H        38 SO.sub.3 H SO.sub.2 C.sub.6 H.sub.5 H H SO.sub.2 CH═CH.sub.2 H        39 H SO.sub.2 CH═CH.sub.2 H SO.sub.3 H SO.sub.2 C.sub.6 H.sub.5 H        40 SO.sub.2 C.sub.6 H.sub.5 H H H SO.sub.2       CH═CH.sub.2 H                                                  41 H       ##STR48##       H H SO.sub.2       CH═CH.sub.2 H

                                      TABLE 2                                      __________________________________________________________________________       #STR49##                                                                       -                                                                            Ex. No.           Z.sup.1             Z.sup.2                                  __________________________________________________________________________     42                C.sub.2 H.sub.5     C.sub.2 H.sub.5                            43 C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 OH                                       44 C.sub.2 H.sub.5 C.sub.2 H.sub.4 OH                                          45 C.sub.4 H.sub.9 C.sub.4 H.sub.9                                             46 C.sub.2 H.sub.4 OH C.sub.4 H.sub.9                                           - 47                                                                                                                C.sub.4 H.sub.9                           - 48 C.sub.4 H.sub.9 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                    __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________       #STR51##                                                                        -                                                                           Ex. No.           Z.sup.1             Z.sup.2                                  __________________________________________________________________________     49                C.sub.2 H.sub.5     C.sub.2 H.sub.5                            50 C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 OH                                       51 C.sub.2 H.sub.5 C.sub.2 H.sub.4 OH                                          52 C.sub.4 H.sub.9 C.sub.4 H.sub.9                                             53 C.sub.2 H.sub.4 OH C.sub.4 H.sub.9                                           - 54                                                                                                                C.sub.4 H.sub.9                           - 55 C.sub.4 H.sub.9 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                      56 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH C.sub.4 H.sub.9                         57 CH(CH.sub.3).sub.2 C.sub.2 H.sub.5                                           - 58                                                                                                                C.sub.2 H.sub.5                        __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________       #STR54##                                                                        -                                                                           Ex. No.                                                                             Y.sup.1        Y.sup.2       Y.sup.3                                                                             Z                                       __________________________________________________________________________     59   H              NO.sub.2      H    C.sub.2 H.sub.4 OH                        60 H SO.sub.2 OC.sub.6 H.sub.5 H C.sub.2 H.sub.4 OH                            61 H SO.sub.2 CH═CH.sub.2 H C.sub.2 H.sub.4 OH                             62 SO.sub.2 C.sub.6 H.sub.5 H H C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                                                   - 63                                                                           H SO.sub.3 H                                                                   #STR56##                                 - 64 SO.sub.3 H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H C.sub.2 H.sub.4 OH        65 COC.sub.6 H.sub.5 H H C.sub.2 H.sub.4 OH                                     - 66 H                                                                                                               H C.sub.4 H.sub.9                        - 67 H NO.sub.2 H C.sub.4 H.sub.9                                             68 H NO.sub.2 H C.sub.2 H.sub.5                                              __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________       #STR58##                                                                        -                                                                                                                           Position of                      Ex. No. Y.sup.11 Y.sup.21 Y.sup.31 Y.sup.42 Y.sup.32 Y.sup.22 SO.sub.3       __________________________________________________________________________                                                     H                              69   H          NO.sub.2                                                                              H   H  H          NO.sub.2                                                                              a                                70 H NO.sub.2 H H H NO.sub.2 b                                                  - 71                                                                                                                          SO.sub.3 H H H H                                                             SO.sub.2 CH═CH.sub.2                                                       a                                 - 72                                                                                                                          SO.sub.3 H H H H                                                             SO.sub.2 CH═CH.sub.2                                                       b                                 - 73 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.3 H H H SO.sub.2 CH═CH.sub.2                                                      a                               74 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.3 H H H SO.sub.2 CH═CH.sub.2 b        75 SO.sub.2 C.sub.6 H.sub.5 SO.sub.3 H H H H SO.sub.2 CH═CH.sub.2 b         -                                                                             76 H NO.sub.2 H                                                                                                                H a 61##                        - 77 H NO.sub.2 H                                                                                                             H b 62##                        -                                                                             78 H NO.sub.2 H H                                                                                                              b TR63##                        -                                                                           79   H          SO.sub.2 CH═CH.sub.2                                                              H   H  H          SO.sub.2 CH═CH.sub.2                                                              b                                80 H SO.sub.2 CH═CH.sub.2 H H H SO.sub.2 CH═CH.sub.2 a                  -                                                                             81 H NO.sub.2 H H                                                                                                              bSTR64##                     __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________       #STR65##                                                                        -                                                                           Ex. No.  Y.sup.1          Y.sup.2      Y.sup.3                                                                              Z                                 __________________________________________________________________________     82       H                NO.sub.2     H     C.sub.2 H.sub.5                     83 H NO.sub.2 H C.sub.4 H.sub.9                                                84 H NO.sub.2 H C.sub.2 H.sub.4 OH                                             85 H SO.sub.2 CH═CH.sub.2 H C.sub.2 H.sub.4 OH                             86 H SO.sub.2 CH═CH.sub.2 H C.sub.2 H.sub.5                                87 H SO.sub.2 CH.sub.2 CH.sub.2 OH H C.sub.2 H.sub.5                           88 SO.sub.2 C.sub.6 H.sub.5 H H C.sub.2 H.sub.4 OH                              - 89                                                                                                                       SO.sub.3 H H C.sub.2                                                         H.sub.5                              - 90                                                                                                                       H SO.sub.3 H C.sub.2                                                         H.sub.5                              - 91 H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H C.sub.2 H.sub.4 OH                  - 92 H                                                                                                                     H C.sub.2 H.sub.4 OH                                                           - 93 SO.sub.3 H SO.sub.2                                                     N(C.sub.2 H.sub.5).sub.2 H                                                     C.sub.2 H.sub.5                   __________________________________________________________________________

EXAMPLE 94

29.9 g of 4-phenoxysulfonylaniline were stirred up overnight in 100 ml of concentrated hydrochloric acid. Then 100 g of ice/water and 2 g of an acidic wetting agent were added and the mixture was cooled to 0° C. After this, 37.5 ml of 23% strength by weight aqueous sodium nitrite solution were added dropwise and the mixture was subsequently stirred at 0-5° C. for 30 minutes. Excess nitrous acid was then destroyed and 46 g of 83.2% strength by weight monosodium 1-aminohydroxynaphthalene-3,6-disulfonate, which was dissolved freshly in water at a pH of 6.5, were run in. The pH of the reaction mixture was then raised to 2 with sodium bicarbonate and the mixture was subsequently stirred at this pH for 90 minutes, and subsequently stirred overnight at room temperature. The red dye of the formula ##STR69## was coupled with the equivalent quantity of the tetrazonium salt of the formula ##STR70## in a conventional manner at a pH of 8.5-10. The resulting blue diazonium salt of the formula ##STR71## was coupled at a pH of 7.5-10 with m-phenylenediamine, to give the dye of the formula ##STR72##

The VIS spectrum of this dye (dissolved at pH 4 in water) shows absorption maxima at 475 and 597 nm and a minimum at about 568 nm.

EXAMPLE 95

The dye solution obtained in Example 94 was admixed at room temperature with the equivalent quantity of the diazo component of the formula ##STR73## (prepared by analogy with Example 94) and coupling was carried out at a pH of 10.3-10.5. The resulting dye was precipitated at a pH of 6 and then filtered off with suction. Drying gave 161 g of the dye of the formula ##STR74##

The VIS spectrum (range >350 nm) shows a maximum at 587 nm (at pH 4 and likewise at pH 10).

The dye dyes leather dark blue and penetrates deep into the tissue of the leather, while the dye of Example 94 produces strong black dyeings with good fastness properties on leather.

EXAMPLE 96

The procedure of Example 94 was repeated but using 29.6 g of 4-aminodiphenyl sulfone, giving first the dye of the formula ##STR75## which dyes leather in deep black shades; λ max (in H₂ O) at pH 4:595 nm.

When the diazo component of the formula ##STR76## was coupled with this dye at a pH of 10-10.8, the resulting polyazo dye had the formula ##STR77## and also contained a small quantity of the dye of the formula ##STR78##

Dissolved in water at a pH of 4, the mixture has the following UV-VIS spectrum:

λ max=485 nm and 591 nm.

The dye dyes leather in a gray shade.

EXAMPLE 97

29.1 g of the diazo component of the formula ##STR79## were diazotized as in Example 94 and coupled with 46 g of 83% strength by weight monosodium 1-amino-8-hydroxynaphthalene-3,6-disulfonate. The resulting red dye of the formula ##STR80## was admixed with 0.12 mol of the tetrazonium salt of the formula ##STR81## and coupling was carried out with a pH of 7-10 to give the blue diazonium salt of the formula ##STR82##

Then 12.7 g of m-phenylenediamine were added and coupling was carried out at a pH of 9.5 to give the dye of the formula ##STR83##

The resulting green dye solution was admixed with 0.12 mol of the diazonium salt of the formula ##STR84## whose preparation is described in Example 96, and coupling was carried out at a pH of 10-11 to give the dye of the formula ##STR85## a blue-black dye which dyes leather in a fast dark blue shade.

       - The dyes indicated in the Tables below are obtained analogously.       ##STR86##      Ex. No. Z.sup.1 Z.sup.2 Z.sup.3 Z.sup.4 Z.sup.5 Z.sup.6 Hue         98 C.sub.6 H.sub.5 SO.sub.2 NO.sub.2 NH.sub.2 NH.sub.2 H H blue-green         99 C.sub.6 H.sub.5 SO.sub.2 NO.sub.2 NH.sub.2 NH.sub.2 H SO.sub.3 H      blue      100       ##STR87##       NO.sub.2 NH.sub.2 NH.sub.2 H H blue      101 C.sub.2 ═CHSO.sub.2 C.sub.6 H.sub.5 SO.sub.2 NH.sub.2 NH.sub.2 H        H blue-gray      102       ##STR88##       NO.sub.2 NH.sub.2 NH.sub.2 H H blue-gray      103       ##STR89##       NO.sub.2 OH NH.sub.2 H H cloudy blue      104 NO.sub.2 CH.sub.2 ═CHSO.sub.2 OH NH.sub.2 H H cloudy blue              105 NO.sub.2 H NH.sub.2 NH.sub.2 C.sub.6 H.sub.5 SO.sub.2 H      blue-gray      106       ##STR90##       NO.sub.2 NH.sub.2 NH.sub.2 H H blue-gray      107 CH═CHSO.sub.2 NO.sub.2 OH NH.sub.2 H H blue-gray      108 CH.sub.2       ═CHSO.sub.2                                                   ##STR91##       NH.sub.2 NH.sub.2 H H blue-gray      109 CH.sub.2 ═CHSO.sub.2 H NH.sub.2 NH.sub.2 C.sub.6 H.sub.5      SO.sub.2 H blue-gray        110 CH.sub.2 ═CHSO.sub.2 H NH.sub.2 NH.sub.2 C.sub.6 H.sub.5      SO.sub.2 SO.sub.3       H cloudy blue                                           111 NO.sub.2 H      NH.sub.2 NH.sub.2 C.sub.6 H.sub.5 SO.sub.2 SO.sub.3 H cloudy blue              112 NO.sub.2 H NH.sub.2 OH C.sub.6 H.sub.5 SO.sub.2 SO.sub.3 H      cloudy blue        113 NO.sub.2 SO.sub.3 H NH.sub.2 NH.sub.2 C.sub.6 H.sub.5 SO.sub.2 H      cloudy blue        114 NO.sub.2 C.sub.6 H.sub.5 SO.sub.2 NH.sub.2 NH.sub.2 H SO.sub.3 H      gray-blue      115 NO.sub.2 SO.sub.3       H NH.sub.2 NH.sub.2                                                   ##STR92##       H gray-blue      116 CH.sub.2 ═CHSO.sub.2 SO.sub.3       H NH.sub.2 NH.sub.2                                                   ##STR93##       H gray-blue      117 CH.sub.2 ═CHCH.sub.2 SO.sub.2 SO.sub.3 H NH.sub.2 NH.sub.2       ##STR94##       H gray-blue      118 CH.sub.2 ═CHSO.sub.2 SO.sub.3 H NH.sub.2 NH.sub.2 C.sub.6      H.sub.5       SO.sub.2 H gray-blue            119 NO.sub.2 SO.sub.3       H NH.sub.2 NH.sub.2                                                   ##STR95##       H gray-blue      120 CH.sub.2 ═CHSO.sub.2 SO.sub.3 H NH.sub.2 NH.sub.2 C.sub.6      H.sub.5       SO.sub.2 H gray-blue                                              121      NO.sub.2 SO.sub.3 H OH NH.sub.2 C.sub.6 H.sub.5 SO.sub.2 H gray-blue           122 NO.sub.2 SO.sub.3 H NH.sub.2 OH C.sub.6 H.sub.5 SO.sub.2 H      gray-blue

                                      TABLE 6                                      __________________________________________________________________________       #STR96##                                                                        -                                                                           Ex. No.        Z.sup.1      n            Z.sup.2  Hue on leather               __________________________________________________________________________       123                                                                                                                              0 H black                     - 124 (CH.sub.3 OCH.sub.2 CH.sub.2)NSO.sub.2 0 H black                         - 125                                                                                                                           0 H black                     - 126                                                                                                                           1 H dark blue                                                                  - 127 (CH.sub.3                                                              OCH.sub.2 CH.sub.2)NSO.s                                                       ub.2 1 H dark blue                                                               - 128                                                                          1 H dark blue                                                                  - 129                                                                          0 H black                     - 130                                                                                                                           1 H black                     - 131                                                                                                                           0 H black                     - 132                                                                                                                           0 H black                     - 133 C.sub.6 H.sub.5 SO.sub.2 0 SO.sub.3 H black                             134 O.sub.2 N 1 H blue-gray*)                                                __________________________________________________________________________      *).sub.max 593 nm (pH ˜ 4, in water), shoulder at 500 nm            

We claim:
 1. A polyazo dye of the formula I ##STR105## where n is 0 or 1,Y¹ is hydrogen, hydroxysulfonyl, pyrrolidinylsulfonyl, pi-peridinylsulfonyl, morpholinylsulfonyl or SO₂ --Alk, SO₂ --Ar, SO₂ --N(Alk)₂, SO₂ --N(Alk)Ar, SO₂ --OAr, SO₂ --C₂ H₄ --Q, SO₂ --CH═CH₂, SO₂ --CH₂ CH═CH₂, CO--Ar, ##STR106## Y² is nitro, SO₂ --NHAr or Y¹, Y³ is hydrogen, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula SO₂ --Alk, SO₂ --N(Alk)₂, SO₂ --NHAlk, SO₂ --CH₂ COOH, SO₂ --C₂ H₄ --Q, SO₂ --CH═CH₂, SO₂ --CH₂ CH═CH₂, CO--Ar or C--NHAlk or Y³ and Y² together are L--NZ--CO, Y⁴ is hydrogen, or Y⁴ and Y³ together are L--NZ--CO, X is hydrogen or C₁ -C₄ -alkyl, R¹ is hydrogen, C₁ -C₄ -alkyl, halogen, carboxyl, C₁ -C₄ -alkoxycarbonyl or hydroxysulfonyl, R² is hydrogen, C₁ -C₄ -alkyl, halogen, carboxyl or C₁ -C₄ -alkoxycarbonyl, or R² and R¹ together are L--NZ--CO, R³ is hydrogen, hydroxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkanoyloxy or benzoyloxy, and R⁴ is hydrogen, amino or hydroxyl, where Alk is C₁ -C₈ -alkyl which may be interrupted by 1-3 oxygens in ether function or by sulfur or sulfonyl and may be substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carboxyl or phenyl, Ar is phenyl which may be substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, carboxyl, C₁ -C₄ -alkanoylamino or hydroxysulfonyl, L is methylene or carbonyl, Z is hydrogen, naphthyl, C₅ -C₈ -cycloalkyl, Alk or Ar, and Q is hydroxyl or a group which may be eliminated under alkaline conditions.
 2. A polyazo dye as claimed in claim 1, of the formula Ia ##STR107## where Y¹, Y², Y³, Y⁴, X, R¹, R² and R³ are each as defined in claim
 1. 3. A polyazo dye as claimed in claim 1, of the formula Ib ##STR108## where Y¹, Y², Y³, Y⁴ ₁ X, R¹, R² and R³ are each as defined in claim
 1. 4. A polyazo dye as claimed in claim 1, wherein R¹ and R² are each hydrogen.
 5. A polyazo dye as claimed in claim 1, wherein R³ is hydroxyl.
 6. A polyazo dye as claimed in claim 1, wherein X is hydrogen.
 7. A polyazo dye as claimed in claim 1, wherein Y¹ is hydrogen, hydroxysulfonyl or ##STR109## where each Ar is as defined in claim
 1. 8. A polyazo dye as claimed in claim 1, wherein Y² is hydrogen, hydroxysulfonyl, nitro or SO₂ --N(Alk)₂, SO₂ --C₂ H₄ --Q or SO₂ --CH═CH2, where Alk and Q are each as defined in claim
 1. 9. A polyazo dye as claimed in claim 1, wherein Y³ is hydrogen, hydroxysulfonyl or SO₂ --C₂ H₄ --Q or SO₂ --CH═CH₂, or Y³ and Y² together are L--NZ--CO, where L, Q and Z are each as defined in claim
 1. 10. A method of dyeing natural or synthetic substrates, which comprises applying to said substrates one or more polyazo dyes as claimed in claim
 1. 